Applied Surface Science 258 (2012) 74707479

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Applied Surface Science

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Surface modication of Cameroonian magnetite rich clay with Eriochrome Black T. Application for adsorption of nickel in aqueous solution
Paul Djomgoue , Mermoz Siewe, Emmanuel Djoufac, Pascalin Kenfack, Daniel Njopwouo
Laboratoire de physico-chimie des matriaux minraux, dpartement de chimie inorganique, Universit de Yaound I. B.P. 812 Yaound, Cameroon

a r t i c l e

i n f o

a b s t r a c t
In this study, the surface of Cameroonian magnetite rich clay was modied using Eriochrome Black T, EBT by the batch adsorption method. The EBT-modied magnetite rich clays were used for nickel ions adsorption from aqueous solution. The effect of various experimental factors; the pH of solution, the inuence of concentration, the temperature, the contact time and the particle size of the sample were studied by using the batch technique. Adsorption process was better described by the pseudo-secondorder kinetic and Tempkin isotherm model. The results showed that the EBT adsorption onto samples is affected by the pH of solution and the maximum EBT ion adsorption takes place between pH 2 and pH 3. The characterization of the surface modication was performed with FTIR and ZPC measurements. The FTIR shows that chemisorption took place at the surface of the bulk samples. The EBT-modied magnetite rich clay presented a binding capacity of nickel ions about 30% higher compared to the unmodied samples from an initial nickel ions concentration of 5.26 mmol using 0.5 g of sample. 2012 Elsevier B.V. All rights reserved.

Article history: Received 14 November 2011 Received in revised form 9 April 2012 Accepted 10 April 2012 Available online 17 April 2012 Keywords: Clay Magnetite Eriochrome Black T Adsorption Nickel (II)

1. Introduction Heavy metals like nickel, cobalt and others, are found in wastewater from chemical manufacturing, painting and coating, mining, extractive metallurgy, nuclear and other industries [1]. Dyes are widely used in industries such as textiles, pulp mills, leather, dye synthesis, printing, food, and plastics, etc. These pollutants constitute serious problems to human health and environment. For example the main symptoms of nickel are headaches, dizziness, nausea and vomiting, chest pain, tightness of the chest, dry cough and shortness of breath, rapid respiration, cyanosis and extreme weakness [2]. Therefore the removal of nickel ions or dyes from wastewater is required for human living and environment, which has been extensively investigated in industries [312]. A number of methods are available for the removal of metal ions from aqueous solutions these are: ion exchange [3], solvent extraction [4], reverse osmosis [5], precipitation [6], coagulation and occulation [7], and adsorption [8]. The adsorption process has been the most frequently applied method in the industries consequently being the most extensively studied one. A number of scientists for this purpose have used different adsorbents such as charcoal [9], zeolites [10], baggase [11], y ash [12], clay, etc. The major drawback of this method is the high price of adsorbents which increase the cost of treatment. The challenge is to develop

Corresponding author. E-mail address: djomgouep@gmail.com (P. Djomgoue). 0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2012.04.065

low cost and efcient adsorbents for the removal of heavy metal or dyes from wastewater. For that reason more attention has been focused on the development of low cost adsorbents for the purication of waste water using clays or clay materials. The use of clays as adsorbents has advantages over commercially available adsorbents in terms of low-cost, an abundant availability, the high adsorption properties, the high specic surface area, non-toxicity, and large potential for ion exchange [13]. The adsorption of cationic dyes onto kaolinite [14], and heavy metals from solution onto palygorskite [15] are some of the examples. Many other works have dealt with this subject [1621]. Magnetic particles have been used to remove a number of chemical species from aqueous efuents. When the adsorption process is carried out, the adsorbent can be separated from the aqueous medium by a simple magnetic process [22]. However, these materials suffer from small surface areas or small adsorption capacity, which limits their application. Some studies indicated that clay minerals and natural magnetite, modied by organic compounds, are suitable materials for ions retention [23]. Therefore there has been much interest in the use of organo-clay as adsorbent to prevent and remediate environmental contamination. The organic chelates or ligand have the tendency to form metal complexes with various metal ions in solution and when these chelates are grafting on suitable support play a very important role in the preconcentration as well as the separation of heavy metal in aqueous solution [24]. In 1997, Mahmoud [25] studied the immobilization of Eriochrome Black T, EBT on silica surface via 3chloropropyltrimethoxysilane as extractor of Zn2+ , Mg2+ and Ca2+

P. Djomgoue et al. / Applied Surface Science 258 (2012) 74707479 Table 1 Chemical and physical characteristics of samples. Kob Granulometric ( m) Percentage (%) pH pHH2 O pHKCl ZPC Mineralogy (%) Kaolinite Halloysite Magnetite Goethite Total nd: not deterninated. 0100 100 5.96 6.55 6.6 45 24 16 13 98 Mag 20100 80 6.65 7.03 7.1 25 22 48 nd 95 Methods Robisons pipette [28] Table 2 Characteristics of EBT. Characteristics

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OH N

HO N

O S Na O N O

Potentiometric [29] X-ray diffraction [27,30]

in aqueous solution. He also investigated the effect of pH and ionic strength. More recently, Barka et al. [26] have also removed EBT in aqueous solution by biosorption using scolymus hispanicus as bioadsobant. In this present study, natural magnetite rich clay from Bafang, a western region of Cameroon was selected as an adsorbent. The rst objective of this study was to evaluate the adsorption of EBT on this material; the effects of parameters such as the pH of EBT solution, the contact time, the temperature and the particle size of the adsorbent on the EBT adsorption capacity were investigated. After the adsorption process of EBT, these materials have been characterized by FTIR and the zero of point charge, ZPC. The EBT-modied clay surfaces were used for the extraction of nickel ions from aqueous solutions and to compare the results to the bulk samples which constitute the second objective of this study. The different adsorption kinetic and isotherm models which describe the adsorption of EBT or nickel ions on the magnetite rich clay were presented. 2. Material and methods 2.1. Material The bulk sample was denoted Kob, the fraction >20 m mainly Mag was obtained after the elimination of the fraction <20 m by siphonation following the Stockes law. The characterization of these samples was introduced by our previous study [27]. The Table 1 shows some chemical and physical characteristics of these samples. 2.2. Chemicals The EBT, sodium 1-(1-hydroxy-2-naphthylazo)-2-naphthol-4sulphonate was purchased from Reagenzien Merck. Table 2 gives some characteristics of this dye, NiCl2 6H2 O was obtained from the Riedel De Haen AG. All these reagents were used without further purication. 2.3. Adsorption experiments 2.3.1. Preparation of the adsorbent material The clay sample was rst dried and sieved through a 100-mesh, then washed with distilled water several times to remove any dust and other water-soluble impurities. The washed sample was dried at room temperature. 2.3.2. Adsorption procedure The clay samples were weighed with the accuracy of 0.01 g and transferred to conical asks with glass stoppers. Adsorption kinetic experiments were carried out using a magnetic stirrer of 50 mL solution with EBT (50 mg/L) at 24 1 C, pH 5.6

Structure Molar mass (g/mol) Index color pK Color Formula Solubility in water
max

461.38 C.I 14645 6.3, 11.5 Red below pH 5.5 and blue between 7 and 11 C20 H12 N3 O7 SNa 50 g/L (20 C) 526 nm at pH below 5.5

by adding 1.00 g of sample at constant stirring speed during 5, 10, 15, 20, 30, 40 and 60 min. The concentrations of EBT in the aqueous solutions were determined by using Corning 529 spectrophotometer at 525 nm after 24 h of decantation following by ltration using lter paper. The effect of initial pH of the dyes solution was investigated at pH 2, 3, 4, 5, 6, 7, 8, 9, and 10. 1.00 g sample of clay was added to 50 mL volume of EBT in aqueous solution having an initial concentration of 50 mg/L for a constant adsorption time of 25 min. The pH of the solution was adjusted to the required value by using HCl (2 103 M) or NaOH (2 103 M) solution. In the investigation of pH, due to shift in the max value, the new max was determined by scanning the samples in a range of 300800 nm. Two samples of Kob and Mag were modied with EBT at the concentrations 50 and 100 mg/L and noted Kob50 and Kob100 also Mag50 and Mag100 respectively for Kob and Mag. The samples were subsequently washed with distilled water after the adsorption until the ltrate showed no trace color of suspended. The adsorption mechanisms were carried out by preparing nickel ions. Adsorption of nickel ions was determined by batch experiment by adding 0.50 g of a pure clay sample or a modied sample with 50 mL of aqueous nickel solution (5.26 mmol) in 250 mL conical ack at pH 2. The mixture was shaken for a given time, and then the suspension was taken after 24 h of decantation. The initial and the nal concentration of nickel ions in the solution were measured using the Corning 529 spectrophotometer at max = 395 nm. The effect of temperature on adsorption of EBT and nickel ions was investigated different temperatures, i.e. 25, 40 and 60 C using 1 g of samples in 50 mL solution of EBT or Nickel ions respectively with 50 mg/L and 5.26 mmol. All assays were carried out in triplicate and only average values were presented. The percentage adsorbed, E% was calculated using the relation (1): E% = 1A A0 100 (1)

A0 and A are the initial and nal concentrations of the ion (EBT or nickel ions) before and after the adsorption, respectively. 2.4. Characterization The samples were characterized by Fourier Transform Infrared (FTIR) spectroscopy (Bruker Alpha-p) in the spectral range of 10004000 cm1 . The zero point of charge, ZPC of samples was determined as described by Al-Harahsheh et al. [29]. A xed mass of sample was introduced into six 100 ml Erlenmeyer asks containing 50 ml of

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0.1 M potassium nitrate solution. The initial pH of these solutions was adjusted to 2, 4, 6, 8, 10, and 12 by using negligible amount of dilute nitric acid or potassium hydroxide. Each solution was allowed to equilibrate for 24 h in an isothermal shaker at 2325 C. The suspension was ltered and the nal pH of this suspension was measured again. 3. Model tting

The effect of intraparticle diffusion resistance on adsorption can be determined by the following relationship [37]: qt = kip t 1/2 + C (7)

kip is the intraparticle diffusion rate constant (mg g1 min1/2 ). To follow the intraparticle diffusion model, a plot of qt against t1/2 show yields a linear line where the slope is kip . 3.2. Adsorption isotherm

3.1. Adsorption kinetics Adsorption characteristics of the equilibrium data and adsorption kinetics, describe how pollutants interact with adsorbent materials are very important for the optimization of adsorption systems. In order to investigate the mechanism of adsorption, the pseudo-rst-order kinetics model, the pseudo-second-order kinetics model, the Elovich model and the intraparticle diffusion model were used to test the dynamical experimental data. 3.1.1. The pseudo-rst-order equation ln(qe qt ) = ln qe k1 t The equilibrium behavior of adsorption of EBT ion on clay samples can be mathematically expressed via proper equations of adsorption isotherms. For that reason four common adsorption isotherms, namely Freundlich, Langmuir (rst and second version), Tempkin and DubininRadushkevich (DR) isotherms are using. These isotherms are described below. 3.2.1. The Freundlich isotherm The Freundlich adsorption isotherm equation is given by Eq. (8) qe = kF Ce
1/nf

(2)

(8)

qe and qt are the amounts of dye (mg/g) adsorbed on the clay at equilibrium and at time t, k1 is the rate constant (min1 ). The rate constant, k1 was obtained from slope of the linear plots of ln(qe qt ) against t [34]. 3.1.2. The pseudo-second-order rate equation t 1 1 = + t qt qe k2 q2 e

The logarithmic form of the Eq. (8) becomes: ln qe = log kF + 1 ln Ce nF (9)

(3)

k2 is the rate constant of pseudo-second-order adsorption. If the initial adsorption rate is [34]: h= 1 k2 q2 e (4)

The Freundlich adsorption isotherm represents the equilibrium relationship between the amount of ion (nA , mmol) adsorbed per unit mass of adsorbent (ms, g) and the concentration of ion Ce, mg L1 . kF and nF are Freundlich constants related the adsorption capacity and the intensity of adsorption, respectively. The value of capacity qe at Ce can be calculated by the equation below. qe = (C0 Ce )VL ms (10)

then Eq. (3) becomes t =h+ qt 1 qe t (5)

Detailed descriptions of Eq. (10) were summarized as follows, C0 = 50 mg L1 , initial concentration of EBT ion in solution, Ce : equilibrium concentration of EBT ion in solution (mg L1 ), VL : volume of solution (0.05 L in this study), ms : mass of solid adsorbent, qe is the amount of dye adsorbed on the solid at equilibrium (mmol g1 ). 3.2.2. The Langmuir isotherm The Langmuir equation is: qe = qmax KL Ce 1 + KL Ce (11)

The equilibrium adsorption capacity qe , the initial adsorption rate h and also the second-order rate constant, k2 (mg g1 min1 ) can be determined experimentally from the slope and intercept of the plot of t/qt against t. 3.1.3. The simplied Elovich equation 1 1 qt = + ln() ln t

(6)

where (mg g1 min1 ) is the initial adsorption rate constant and the parameter (g mg1 ) is related to the extent of the surface coverage and activation energy for chemisorption [35,36]. The values of and can be calculated from the plot of qt against 1/ln t. 3.1.4. Intraparticle diffusion model Intraparticle diffusion can be described by three consecutive steps: (i) The transport of adsorbate from the bulk solution to the outer surface of the adsorbent by molecular diffusion. (ii) The internal diffusion, the transport of adsorbate from the particles surface into interior sites. (iii) The adsorption of the solute particles from the active sites into the interior surface of the pores.

where qe and Ce are the equilibrium concentrations of adsorbate on solid and in liquid, respectively. qmax and KL represent the monolayer adsorption capacity and the equilibrium constant of adsorption, respectively. Eq. (11) can be rearranged as the rst version at Eq. (12): 1 (1/qmax ) = qe 1 + KL Ce or the second version at Eq. (13) 1 1 1 = + qe qmax KL qmax Ce (13) (12)

From the linear plots of Ce /qe versus Ce (rst version) or 1/qe versus 1/Ce (second version) we can obtain the parameters qmax and KL of Eq. (11) 3.2.3. Tempkin model Tempkin and Pyzhev [40] considered the effects of some indirect adsorbateadsorbate interactions on adsorption isotherms and suggested that the heat of adsorption of all the molecules in the

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Fig. 1. The kinetic adsorption of EBT on Kob and Mag surface at pH 5.6; T = 25 C; the volume of solution is 50 ml, C0 = 50 mg/L.

adsorbed layer would decrease linearly with the coverage. The Tempkin isotherm equation is given by the Eq. (14). qe = RT ln(KT Ce ) b (14)

Fig. 2. Effect of pH of medium on EBT adsorption at initial concentration 50 mg/L, V = 50 mL, during 25 min of treatment.

the linear form of Eq. (14) is: qe = B1 ln KT + B1 ln Ce where B1 = RT b (16) (15)

into different types of adsorbents as for example montmorillonite [31] or kaolinite [32]. It seems that the adsorption of dye was more efcient for Kob than Mag sample at this pH because Kob adsorbs 85% compare to Mag which adsorbs 60% from a solution of 50 mg/L of EBT.

The adsorption data can be analyzed according to Eq. (15). A plot of qe versus ln Ce enables the determination of the isotherm constants KT and B1 . The constant B1 is related to the heat of adsorption (J mmol1 ). 3.2.4. DubininRadushkevich, (DR) isotherm The DR isotherm is more general than the Langmuir isotherm because it does not assume a homogenous surface or a constant sorption potential [41]. The DR equation is: ln Ct = ln cm B2 (17)

4.2. Effect of pH The solution pH has an important effect on dye adsorption. It inuences the surface charge of the adsorbent, the degree of ionization of the material present in the solution and the dissociation of functional groups on the active sites of the adsorbent. In addition it affects the solution of the dying chemistry. The effect of pH EBT solution, at an initial concentration of 50 mg/L is shown in Fig. 2. The adsorption capacities of the samples decreased with an increasing of the pH, the adsorption shows a maximum takes between pH 2 and pH 3. This observation can be explained by the chemical composition of the samples (Table 1). In fact between pH 2 and pH 3, Mag fraction was more efcient than Kob sample certainly by its rich content in magnetite mineral, the surface of magnetite ( FeOH) can be protoned ( FeOH2+ ) and improve the attraction with the SO3 group of EBT (Scheme 1a). At a pH above 3, Mag exhibits the lower afnity for this dye than Kob due to the decrease of protoned surface form of magnetite which have its neutral pH at 6.8, on the other hand, the Kob sample contains goethite and this mineral has the ZPC far at 9.1 [33], this mineral could be responsible for the increasing of adsorption at this pH. Above the ZPC, the surface material is deprotonated ( FeO ) and the adsorption is certainly realized by the hydrogen bond between the OH group of EBT and deprotoned surface ( FeO ) of material (Scheme 1b) and less efcient than in acid medium. This is probably due to the repulsion between the FeO and the SO3 group of EBT.

where Cm is the maximum amount of adsorbed solute, B is a constant related to the adsorption energy by Eq. (19) and is given by: = RT ln 1 + 1 Ce (18)

The values of Cm and B, can be determined from the intercept and the slope of plot of ln Ct versus 2 . The mean adsorption energy, E which is the free energy of transfer of 1 mole of solute from innity (bulk solution) to the surface material [42], given by the Eq. (19): E= 1 (2B)1/2 (19)

4. Results and discussion 4.1. Effect of contact time The contact time is one of the important parameters for the successful application of adsorption procedures. The adsorption of EBT on Kob and Mag as a function of the contact time at pH 5.6 0.2 in order to nd out the equilibrium time for maximum adsorption was carry out. Fig. 1 shows the adsorption of EBT; percentage (%) was derived from the difference of the initial and nal concentration (C0 , mg/L) and (Ce , mg/L), respectively. The rapid adsorption observed during the rst 15 min was probably due to the abundant availability of active sites on the clay surface, and with the gradual occupancy of these sites. The adsorption of EBT reached equilibrium after about 20 min for both samples. Similar behaviors were previously reported in the literature about dye adsorption experiments

4.3. Adsorption kinetic analysis of EBT on Kob and Mag samples The parameters calculated for the different models are given in Table 3. The kinetic data obtained gave poor tting with the Elovich and the intraparticle diffusion model for the Mag sample. A good tting was obtained with pseudo-second-order model as shown by the high correlation coefcient. The calculated amount of dye adsorbed at equilibrium (qe ) is very close to the experimentally obtained value. Thus, the adsorption of EBT on Kob and Mag can be explained by the pseudo-second-order kinetic model. This suggests that the EBT adsorption process appears to be controlled by the chemical reaction [38,39].

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Scheme 1. Possible interactions between the surface material and the EBT molecule, where S represents the active surface functional groups including the silanol (Si O ), aluminol (Al O ) and irinol (Fe O ) sites; S OH and S O refer to neutral and ionized surface hydroxyl functional groups.

Table 3 Kinetic model constants for the adsorption of EBT on Kob and Mag samples at pH 2 at initial concentration 50 mg/L, V = 50 mL, during 25 min of stirring. Pseudo-rst order model K1 (min Kob Mag 0.033 0.069
1

Pseudo-second order model

1

qe (mg g 0.124 0.034

K2 (g mg1 min1 ) 9.1 103 14 102

qe (mg g1 ) 33 103 74 103 Elovich model

h (mg g1 min1 ) 109.09 7.85

r2 0.988 0.933

0.975 0.925

Intraparticle diffusion model Kip (mg g Kob Mag 0.035 0.029

1

min

1/2

C (mg g 0.172 0.181

(mg g1 min1 ) 1.8 10 1.8 1076

88

(g mg1 ) 172.41 200.05

r2 0.954 0.822

0.916 0.845

4.4. Analysis of adsorption isotherms of EBT on Kob and Mag samples The parameters of Freundlich, Langmuir rst and second version, DubininRadushkevich (DR), and Tempkin adsorption isotherms of EBT on Kob and Mag samnples at pH value 2 are listed in Table 4. The values of kF in Freundlich isotherms at pH 2 indicated an afnity for EBT on Kob and Mag samples; this afnity is greater for the Mag sample than the Kob sample due to the higher value of kF for Mag. Furthermore, the value of nF of these samples was greater than 1, indicating favorable adsorption. The Freundlich isotherm yielded a good t to experimental data for EBT adsorption on Kob and Mag samples. However, at pH 2, the values of qL derived from the results of Langmuir isotherm were negative and irrational for physical interpretation. Thus, the Langmuir equation was not applicable for the cases at pH 2 adsorption of the EBT ions on the both samples [43,44]. The Table 4 indicates that the best t was obtained by the Tempkin model with high correlation coefcients (r2 > 0.999).

Table 4 Rate coefcients of models describe EBT adsorption on studied material at pH 2 at initial concentration 50 mg/L, V = 50 mL, during 25 min of stirring. Constant Freundlich 1/nF KF (L mmol1 ) r2 Langmuir 1st version qmax (mmol g1 ) KL (L g1 ) r2 Langmuir 2nd version qmax (mmol g1 ) KL (L g1 ) r2 Tempkin B1 (J mmol1 ) KT (L mmol1 ) r2 Kob 0.423 0.997 0.992 0.39 0.714 0.985 0.399 0.689 0.997 4.7 103 0.999 0.998 Mag 0.600 2.860 0.972 2.136 0.102 0.975 0.978 0.162 0.985 2.5 103 0.998 1.000

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Table 5 Vibration band position and their assignments for Mag, Kob, Mag100 and Kob100. Band position (cm1 ) Original band (bulk samples) Mag 3688 3648 999 901 524 414 Kob 3690 3627 1540 991 904 528 423 Al OH Al (multiple bands) Stretching vibration of hydroxyl group (kaolinite) O H water [48] Si O, tetrahedral Si O vibration Al OH, octahedral Al OH Fe O magnetite [49] Si O, Si O Si vibration Possible assignments of group present Possible assignments of group present

Band position (cm1 )

New band (functional samples) Fig. 3. FT-IR spectra of Mag100 and Mag. Mag100 3701 3666 3614 3597 1614 1596 1490 Kob100 3673 1644 1604 1490 Surface hydroxyl group Surface hydroxyl group O H water stretching vibration O H water bending vibration C C aromatic symmetric vibration SO3 group

4.5. Inuence of temperature of EBT adsorption on Kob and Mag sample The adsorption capacities of Kob and Mag samples at different temperatures (25, 40 and 60 C) as a function of time were investigated at an initial EBT concentration of 50 mg L1 by batch contact-time experiments. A larger amount of EBT was removed by clay in the rst 10 min of contact time. Adsorption equilibrium was reached within 20 min at the end of rapid adsorption for all temperatures studied. In this study it was observed that the temperature has signicant effect on the adsorption of EBT dye for Kob and Mag samples due to the fact that the yield of EBT adsorption on these materials increase with the increase of temperature. The temperature can be an origin of additional adsorption reactive sites on surfaces which increase the adsorption capacity of samples. The same observations were previously reported in the literature [45,46]. 4.6. Characterizations 4.6.1. FT-IR spectra The Figs. 3 and 4 show the FTIR spectra of Mag, Kob, Kob100 and Mag100. Table 5 gives the vibration band position and their assignments. The bands 3688, 3648 cm1 for Mag and 3690 and 3627 cm1 for Kob can be attributed to the hydroxyl groups on the surface material. The double peaks at 3701 and 3666 cm1 were due to the stretching vibrations of inner surface hydroxyl groups. The band at 1644 cm1 is the OH bending vibration and stretching vibration of water molecules in the interlayer of the clay. After the adsorption of EBT, new characteristic bands were observed at 3701, 3614, 3597, 1614, and 1596 cm1 for Mag100 and 3673, 1644, 1604 and 1490 cm1 for Kob100. They could be attributed in some cases to the organic grafted molecules [47]. On

the other hand molecules containing NO2 groups commonly exhibit an asymmetric and a symmetric stretching vibration of the NO2 group from 1660 to 1500 cm1 , therefore the band at 1596 cm1 can be assigned to the NO2 group. The peak at 1604 cm1 can be assigned to C C aromatic of EBT [50]. A new peak at 1490 cm1 corresponds to SO3 groups. In additional the intensities of the hydroxyl groups for modied samples have reduced in comparison to their intensities on raw material; this conrms that surface hydroxyl groups of raw materials are involved in the adsorption and immobilization of the EBT. 4.6.2. The pH of zero of point charge, pHZPC The pHZPC for a given mineral surface is the pH at which that surface has a net neutral charge. This pHZPC was determined for raw samples and modied samples. Figs. 5 and 6 show these values in terms of the difference in pH solution before and after soaking with potassium nitrate. Untreated samples, Kob and Mag have a pHZPC of 6.6 and 8.2, respectively. After modication these values decreased to 3.7 and 4.5 for Kob and Mag respectively as a result of adsorption EBT ions on the surface. A similar result was obtained in the case of the modication of kaolinite using sodium tetraborate [51]. On the other hand, if the pH of a solution containing the target pollutant under investigation is above the pHZPC of the sample, its surface will have a net negative charge and predominantly exhibit an ability to exchange cations [52]. Consequently,

Fig. 4. FT-IR spectra of Kob100 and Kob.

Fig. 5. The zero of point charge of Kob and the modied samples.

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Fig. 6. The zero of point charge of Mag and the modied samples.

the sample treated with EBT would exhibit a larger potential for the removal of heavy metal in solution than the raw samples. 4.7. Adsorption analysis of nickel ions on Kob, Mag, Kob100 and Mag100 samples This study was carried out by using 50 ml of nickel solution which contains 5.26 mmol of nickel ions for 0.50 g of sample in order to compare the adsorption capacity of different modied clays. The nickel removal capacity for each sample was shown in Figs. 7 and 8. Untreated and modied samples showed similar behaviors for nickel removal ions from the solution and the equilibrium was reached after 1 h for all samples. A short analysis of these gures shows that Kob100 and Mag100 have better capacities on nickel adsorption than the bulk samples, because when these clays were modied with EBT at pH 2,

the removal capacities of these materials were greatly improved. Bulk samples, Kob and Mag can remove respectively about 50% and 60% from 50 ml of nickel solution which contains 5.26 mmol of nickel ions using 0.50 g of sample, take about 25% and 30% more respectively for Kob100 and Mag100 as show in Figs. 7 and 8 in the same conditions. This capacity is certainly due to the higher stability constants of complex formed by Nickel ions with EBT (Scheme 2a) than a complex between the hydroxyl surface and nickel ions (Scheme 2b). The modication on raw materials with EBT increase nickel ions removal capacities due to changes in the surface property of the material. Fig. 9 presents the FTIR spectra of Kobni, KobEni, Magni and MagEni which correspond respectively to Kob, kob100, Mag and Mag100 after nickel ions adsorption. The most important shift is at 1624 cm1 which can be assigned to stretching aromatic or asymmetric stretching of NO2 of EBT. The adsorption through the N N chromophore cannot be completely ruled out, however it seems less probable due to the required necessary deformation of the molecule in order to arrange with the N N bond in the close vicinity of the nickel surface [53]. 4.7.1. Adsorption kinetic analysis of nickel ions on Kob, Kob100, Mag and Mag100 samples In order to investigate the mechanism of adsorption of nickel ions on Kob, Kob100, Mag and Mag100 samples, characteristic constants of adsorption were determined using a pseudo-rst, pseudo-second-order, intraparticle and Elovich model. The result of different parameters is listed in Table 6 on the basis of different correlation coefcients, the results of adsorption kinetics of nickel ions on all the samples show that adsorption process was better described by the pseudo-second-order kinetic, r2 > 0.99. 4.7.2. Adsorption isotherms analysis of nickel ions on Kob, Kob100 Mag and Mag100 samples In the present investigation, the equilibrium data were analyzed using the Freundlich, Tempkin, DubininRadushkevich and Langmuir isotherm expressions; Eqs. (8), (14), (17) and (11), respectively. Figs. 7 and 8 show the dependence of the amount of Nickel ions adsorbed on contact time. The parameters and correlation coefcients of these models for the adsorption of nickel ion on bulk and modied samples were determined from non-linear regression as summarized in Table 7.

Fig. 7. The kinetic absorption of Ni2+ on Kob and modied surface samples with EBT at pH 2; T = 25 C, C0 = 5.26 mmol, vo = 50 mL.

Fig. 8. The kinetic absorption of Ni2+ on Mag and modied surface samples with EBT at pH 2; T = 25 C, C0 = 5.26 mmol, vo = 50 mL.

Fig. 9. FT-IR spectra of Kobni, KobEni, Magni and MagEni which correspond respectively to Kob, Kob100, Mag and Mag100 after Ni2+ adsorption.

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Scheme 2. Mechanic xation of Nickel ions between modied surface (a) and unthreated surface (b). S represents the active surface functional groups including the silanol (Si O ), irinol (Fe O ) and aluminol (Al O ) sites.

Table 6 Kinectic adsorption parameters of Ni2+ on Kob, Kob100, Mag and Mag100 samples at pH 2; T = 25 C, C0 = 5.26 mmol, vo = 50 mL. Pseudo-rst order model K1 (min Kob Kob5o Kob100 Mag Mag50 Mag100 nc nc 3.16 2.22 3.32 3.78
1

Pseudo-second order model

1

qe (mg g nc nc 23.74 9.12 27.66 43.81

K2 (g mg1 min1 ) 2.2 104 1.6 104 4.6 104 0.1 104 62.6 104 8.6 104

qe (mg g1 ) 58.82 31.34 23.92 49.50 2.39 11.44 Elovich model

h (mg g1 min1 ) 1.26 6.28 3.79 29.08 2.85 0.88

r2 0.999 0.999 0.998 0.999 0.996 0.991

nc nc 0.853 0.935 0.993 0.957

Intraparticle diffusion model Kip (mg g Kob Kob50 Kob100 Mag Mag50 Mag100 nc: not calculated 5.01 8.84 5.57 1.62 2.93 5.03
1

min

1/2

C (mg g 103.48 95.53 66.63 62.67 53.98 55.12

(mg g1 min1 ) 8.0 103 70 102 40 103 0.2 105 2.6 103 18 103

(g mg1 ) 0.057 0.043 0.071 0.248 0.125 0.106

r2 0.882 0.968 0.998 0.978 0.882 0.845

0.725 0.909 0.981 0.999 0.844 0.856

Table 7 Adsorption isotherm parameters on Kob, Kob100, Mag and Mag100 samples at pH 2; T = 25 C, C0 = 5.26 mmol, vo = 50 mL. Kob Freundlich 1/n Kf (L mmol1 ) r2 Langmuir rst order qmax (mmol g1 ) Kl (L.g1 ) r2 Langmuir second order qmax (mmol g1 ) KL (L g1 ) r2 Tempkin B1 (J mmol1 ) KT (L mmol1 ) r2 DR B (KJ2 mol2 ) Cm (mmol g1 ) E (kJ mol1 ) r2 1.61 20.2 104 0.969 30.78 0.021 0.959 31.51 0.002 0.883 31.096 2.8.108 0.995 0.065 206.44 2.769 0.904 Kob50 14.52 5653.3 0.983 4.78 0.005 0.991 4.40 0.005 0.9229 47.262 0.001 0.992 0.011 502.70 6.804 0.904 Kob100 0.421 1043.1 0.981 1.668 0.009 0.994 1.51 0.010 0.931 65.648 0.011 0.991 0.003 720.54 12.127 0.903 Mag 1.32 14.9 104 0.998 5.57 0.005 0.999 5.55 0.004 0.995 43.326 8.44.105 0.999 0.017 492.75 5.391 0.994 Mag50 0.365 749.9 0.989 1.367 0.011 0.996 1.29 0.011 0.962 69.751 0.017 0.994 0.003 749.95 12.909 0.954 Mag100 0.215 320.2 0.973 0.432 0.028 0.997 0.34 0.030 0.951 109.07 0.139 0.991 0.001 897.85 28.867 0.937

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The Langmuir isotherm assumes that intermolecular forces decrease rapidly with distance and also that adsorption takes place at specic sites within the adsorbent. The values of qmax of the present study were negative, therefore have no physical explanation. Then the Langmuir isotherms cannot be applied in this case. DubininRadushkevich, The slope and intercept of the plots of ln qe versus 2 give B and Cm , respectively. The value of B is related to sorption energy E, as shown the Eq. (19). The range values of E(212 kJ/mol) for Kob, Kob100 and Mag samples in the present case on nickel ions adsorption is found to be between 8 and 16 kJ/mol (Table 7) which corresponding to physical adsorption [5456]. But the value of E for Mag100 is 28 kJ/mol shows that the chemicals adsorption is involved in this process [57]; this can be explained by Scheme 2. For the Tempkin model the constant B1 related to the heat of adsorption shows the effects of some indirect adsorbateadsorbate interactions on adsorption isotherm, in the present cases these values of B1 are negative. Then there are may be not another interaction about the adsorption of nickel ions on bulk and modied samples. Out of four isotherm models studied for this adsorbentadsorbate system, Tempkin model shows a best t with a good correlation coefcient, r2 > 0.99. 4.7.3. Inuence of temperature of nickel ions adsorption on Kob, Mag, Kob100 and Mag100 samples The adsorption capacities of Kob, Mag, Kob100 and Mag100 at different temperatures (25, 60 and 60 C) as a function of time were investigated at an initial nickel ions concentration of 5.26 mmol. The equilibrium adsorption capacity of nickel ions on Kob, Mag, Kob100 and Mag100 samples increase with the increasing of temperature. The increases of on nickel ions with temperature may be due to an increase in the mobility of nickel ions in the solution with an increase in the temperature or due to the appearance of new sites on the surface material. Therefore, the adsorption process is an endothermic one [58]. 5. Conclusion Our study is one of few investigations into evaluation of natural magnetite rich clay, Eriochrome Black T for the removal of nickel ions from aqueous solution. The adsorption study revealed that a stirring of 20 min is sufcient for the EBT clay material system to reach equilibrium. Based on the results of the experiments the adsorption of EBT is strongly dependent on the pH; the effectiveness is found to be higher between pH 2 and pH 3. The modied samples were characterized using FTIR spectra and the pHZPC. The FTIR conrms that the surface hydroxyl groups are involved in the adsorption and immobilization of the EBT. The kinetic study showed that the adsorption of 50 mL nickel ions (5.26 mmol) using 0.5 g of Kob100 and Mag100 may reach 80% and 90% respectively of the total adsorption capacity in 1 h. The modication of material with EBT increases the adsorption capacity of the nickel ions for 30% compare to the raw materials. Four kinetic models were applied to the experimental data; the most suitable model was the pseudo-second-order model for EBT and nickel ions adsorption. The equilibrium data was analyzed using the Freundlich, Langmuir, Tempkin and DubininRadushkevich models. The adsorption equilibrium data shows that the best t to adsorption is the Tempkin isotherm model. The natural Cameroonian magnetite rich clay has a good potential for the adsorption of EBT molecules. Therefore it may be a promising low cost alternative adsorbent for removing EBT dye from waste water and additionally a suitable adsorbent for wastewater treatment.

Acknowledgements The authors thank the Department of Inorganic Chemistry of the University of Yaounde I, Cameroon which provide the reagents used to carry out this research, Prof. Dr E. Ngameni, Chief of the Department of Inorganic Chemistry of this university for providing the facilities to realize the FTIR. We also thank Tina Obermeit and Gunnar Lahr of Chemnitz Uninersity of Technology, Germany for proof reading.

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